Silicone grafted thermoplastic elastomeric copolymers and hair and skin care compositions containing the same

Abstract

The present invention relates to water or alcohol soluble or dispersible silicone grafted thermoplastic elastomeric copolymers and to cosmetic and pharmaceutical compositions containing these copolymers. This invention especially relates to copolymers useful for hair styling purposes, and to hair styling compositions containing these copolymers. This invention further relates to copolymers useful for providing cosmetic and pharmaceutical compositions for topical application to the skin. These topical skin care compositions are useful for delivering and/or transdermally transporting active ingredients to or through the skin.

What is claimed is: 
     
       1. A hair care composition useful for styling hair, comprising: a) a water or alcohol soluble or dispersible thermoplastic elastomeric copolymer having a backbone and two or more hydrophilic polymeric side chains and one or more polysiloxane side chains, said copolymer formed from the copolymerization of randomly repeating A, B, and C units and corresponding to the formula    A!.sub.a  B!.sub.b  C!.sub.c     wherein   (i) A is at least one monomer unit, copolymerizable with said B and C units, corresponding to the formula ##STR12## wherein X is selected from the group consisting of --OH, --OM, --OR 4 , --NH 2 , --NHR 4 , and --N(R 4 ) 2  ; M is a cation selected from the group consisting of Na+, K+, Mg++, Ca++, Zn++, NH 4  +, alkylammonium dialkylammonium, trialkylammonium, and tetralkylammonium; each R 4  is selected from the group consisting of H, C 1  -C 8  straight or branched chain alkyl, N,N-dimethylaminoethyl, methyl guaternized N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl and 2-ethoxyethyl; and R 5  and R 6  are independently selected from the group consisting of H, C 1  -C 8  straight or branched chain alkyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethyl, and 2-ethoxyethyl;   (ii) B is at least one hydrophilic macromonomer unit, copolymerizable with said A and C units, corresponding to the formula ##STR13## wherein E is an ethylenically unsaturated moiety, copolymerizable with A and C, selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacrloyl, 3-vinylbenzoyl, 4-vinylbenzoyl; R and R' are independently selected from the group consisting of H and C 1  -C 8  straight or branched chain alkyl; and m is an integer from about 10 to about 2000;   (iii) C is at least one polysiloxane macromonomer unit, copolymerizable with said A and B units, corresponding to the formula   E'(Y).sub.n Si(R.sup.7).sub.3-t (Z).sub.t     wherein E' is an ethylenically unsaturated moiety copolymerizable with A and B; Y is a divalent linking group; R 7  is selected from the group consisting of H, lower alkyl, aryl or alkoxy; Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least about 500, is essentially unreactive under copolymerization conditions, and is pendant from said backbone after polymerization: n is 0 or 1; and t is an integer from 1 to 3: and     (iv) a is an integer of about 100 or greater, b is an integer of about 2 or greater, and c is an integer of about 1 or greater; and wherein said A units, in conjunction with said ethylenically unsaturated moieties of said B units and said C units, form said backbone; wherein said polymeric portion of said B units forms said hydrophilic side chains; wherein said polymeric portion of said C units forms said polysiloxane side chains; wherein said copolymer has a weight average molecular weight greater than about 10,000, and wherein said copolymer exhibits at least two distinct T g  values, said first T g  corresponding to said backbone and having a value less than about 0° C. and said second T g  corresponding to said hydrophilic polymeric side chains and having a value greater than about 25° C.; and       b) a carrier suitable for application to the hair.   
     
     
       2. A hair care composition useful for styling hair, comprising; a) a water or alcohol soluble or dispersible thermoplastic elastomeric copolymer having a backbone and two or more hydrophilic polymeric side chains and one or more polysiloxane side chains, said copolymer formed from the copolymerization of randomly repeating A, B, and C units and corresponding to the formula    A!.sub.a  B!.sub.b  C!.sub.c     wherein   (i) A is at least one monomer unit, copolymerizable with said B and C units, corresponding to the formula ##STR14## wherein X is selected from the group consisting of --OH, --OM, --OR 4 , --NH 2 , --NHR 4 , and --N(R 4 ) 2  ; M is a cation selected from the group consisting of Na+, K+, Mg++, Ca++, Zn++, NH 4  +, alkylammonium, dialkylammonium, trialkylammonium, and tetralkylammonium; each R 4  is selected from the group consisting of H, C 1  -C 8  straight or branched chain alkyl, N,N-dimethylaminoethyl, methyl quaternized N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl; and R 5  and R 6  are independently selected from the group consisting of H, C 1  -C 8  straight or branched chain alkyl methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethyl, and 2-ethoxyethyl;   (ii) B is at least one hydrophilic macromonomer unit, copolymerizable with said A and C units, corresponding to the formula ##STR15## wherein R and R' are independently selected from the group consisting of H and C 1  -C 8  straight or branched chain alkyl; and m is an integer from about 10 to about 2000;   (iii) C is at least one polysiloxane macromonomer unit, copolymerizable with said A and B units, corresponding to the formula   E'(Y).sub.n Si(R.sup.7).sub.3-t (Z).sub.t     wherein E' is an ethylenically unsaturated moiety copolymerizable with A and B; Y is a divalent linking group; R 7  is selected from the group consisting of H, lower alkyl, aryl, or alkoxy; Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least about 500, is essentially unreactive under copolymerization conditions, and is pendant from said backbone after polymerization; n is 0 or 1; and t is an integer from 1 to 3; and     (iv) a is an integer of about 100 or greater, b is an integer of about 2 or greater, and c is an integer of about 1 or greater; and wherein said A units, in conjunction with said ethylenically unsaturated moieties of said B units and said C units, form said backbone; wherein said polymeric portion of said B units forms said hydrophilic side chains; wherein said polymeric portion of said C units forms said polysiloxane side chains; wherein said copolymer has a weight average molecular weight greater than about 10,000, and wherein said copolymer exhibits at least two distinct T g  values, said first T g  corresponding to said backbone and having a value less than about 0° C, and said second T g  corresponding to said hydrophilic polymeric side chains and having a value greater than about 25° C.; and       b) a carrier suitable for application to the hair.   
     
     
       3. A hair care composition useful for styling hair, comprising; a) a water or alcohol soluble or dispersible thermoplastic elastomeric copolymer having a backbone and two or more hydrophilic polymeric side chains and one or more polysiloxane side chains, said copolymer formed from the copolymerization of randomly repeating A, B, and C units and corresponding to the formula    A!.sub.a  B!.sub.b  C!.sub.c     wherein   (i) A is at least one monomer unit, copolymerizable with said B and C units, corresponding to the formula ##STR16## wherein X is selected from the group consisting of --OH, --OM, --OR 4 , --NH 2 , --NHR 4 , and --N(R 4 ) 2  ; M is a cation selected from the group consisting of Na+, K+, Mg++, Ca++, Zn++, NH 4  +, alkylammonium, dialkylammonium, trialkylammonium, and tetralkylammonium: each R 4  is independently selected from the group consisting of H, C 1  -C 8  straight or branched chain alkyl, N,N-dimethylaminoethyl, methyl quaternized N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl; and R 5  and R 6  are independently selected from the group consisting of H, C 1  -C 8  straight or branched chain alkyl methoxy ethoxy 2-hydroxyethoxy, 2-methoxyethyl and 2-ethoxyethyl;   (ii) B is at least one hydrophilic macromonomer unit, copolymerizable with said A and C units, corresponding to the formula ##STR17## wherein E is an ethylenically unsaturated moiety, copolymerizable with A, selected from the group consisting of vinyl allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzoyl, 4-vinylbenzoyl, and mixtures thereof; R" is selected from the group consisting of hydrogen and C 1  -C 40  straight or branched chain alkyl; R 3  is selected from the group consisting of H, and C 1  -C 8  straight or branched chain alkyl; and m is an integer from about 20 to about 2000;   (iii) C is at least one polysiloxane macromonomer unit, copolymerizable with said A and B units, corresponding to the formula   E'(Y).sub.n Si(R.sup.7).sub.3-t (Z).sub.t     wherein E' is an ethylenically unsaturated moiety copolymerizable with A and B; Y is a divalent lining group; R 7  is selected from the group consisting of H, lower alkyl, aryl, or alkoxy; Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least about 500, is essentially unreactive under copolymerization conditions, and is pendant from said backbone after polymerization: n is 0 or 1; and t is an integer from 1 to 3; and     (iv) a is an integer of about 100 or greater, b is an integer of about 2 or greater, and c is an integer of about 1 or greater; and wherein said A units, in conjunction with said ethylenically unsaturated moieties of said B units and said C units, form said backbone; wherein said polymeric portion of said B units forms said hydrophilic side chains; wherein said polymeric portion of said C units forms said polysiloxane side chains; wherein said copolymer has a weight average molecular weight greater than about 10,000, and wherein said copolymer exhibits at least two distinct T g  values, said first T g  corresponding to said backbone and having a value less than about 0° C. and said second T g  corresponding to said hydrophilic polymeric side chains and having a value greater than about 25° C.; and       b) a carrier suitable for application to the hair.   
     
     
       4. A composition for topical application to the skin or useful for delivering pharmaceutical actives to the skin, comprising: a) a water or alcohol soluble or dispersible thermoplastic elastomeric copolymer having a backbone and two or more hydrophilic polymeric side chains and one or more polysiloxane side chains, said copolymer formed from the copolymerization of randomly repeating A, B, and C units and corresponding to the formula    A!.sub.a  B!.sub.b  C!.sub.c     wherein     (i) A is at least one monomer unit, copolymerizable with said B and C units, corresponding to the formula ##STR18## wherein X is selected from the group consisting of --OH, --OM, --OR 4 , --NH 2 , --NHR 4 , and --N(R 4 ) 2  ; M is a cation selected from the group consisting of Na+, K+, Mg++, Ca++, Zn++, NH 4  +, alkylammonium, dialkylammonium, trialkylammonium, and tetralkylammonium; each R 4  is selected from the group consisting of H, C 1  -C 8  straight or branched chain alkyl, N,N-dimethylaminoethyl, methyl quaternized N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl; and R 5  and R 6  are independently selected from the group consisting of H, C 1  -C 8  straight or branched chain alkyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethyl, and 2-ethoxyethyl; (ii) B is at least one hydrophilic macromonomer unit, copolymerizable with said A and C units, corresponding to the formula ##STR19## wherein E is an ethylenically unsaturated moiety, copolymerizable with A and C, selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzoyl, 4-vinylbenzoyl; R and R' are independently selected from the group consisting of H and C 1  -C 8  straight or branched chain alkyl; and m is an integer from about 10 to about 2000;   (iii) C is at least one polysiloxane macromonomer unit, copolymerizable with said A and B units, corresponding to the formula   E'(Y).sub.n Si(R.sup.7).sub.3-t (Z).sub.t     wherein E' is an ethylenically unsaturated moiety copolymerizable with A and B; Y is a divalent liking group; R 7  is selected from the group consisting of H, lower alkyl, aryl, or alkoxy; Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least about 500, is essentially unreactive under copolymerization conditions, and is pendant from said backbone after polymerization; n is 0 or 1; and t is an integer from 1 to 3; and     (iv) a is an integer of about 100 or greater, b is an integer of about 2 or greater, and c is an integer of about 1 or greater; and wherein said A units, in conjunction with said ethylenically unsaturated moieties of said B units and said C units, form said backbone; wherein said polymeric portion of said B units forms said hydrophilic side chains; wherein said polymeric portion of said C units forms said polysiloxane side chains; wherein said copolymer has a weight average molecular weight greater than about 10,000, and wherein said copolymer exhibits at least two distinct T g  values, said first T g  corresponding to said backbone and having a value less than about 0° C., and said second T g  corresponding to said hydrophilic polymeric side chains and having a value greater than about 25° C.; and       b) a carrier suitable for application to the skin.   
     
     
       5. A composition according to claim 4 which further comprises a pharmaceutically active agent. 
     
     
       6. A composition for topical application to the skin or useful for delivering pharmaceutical actives to the skin, comprising: a) a water or alcohol soluble or dispersible thermoplastic elastomeric copolymer having a backbone and two or more hydrophilic polymeric side chains and one or more polysiloxane side chains, said copolymer formed from the copolymerization of randomly repeating A, B, and C units and corresponding to the formula    A!.sub.a  B!.sub.b  C!.sub.c     wherein   (i) A is at least one monomer unit, copolymerizable with said B and C units, corresponding to the formula ##STR20## wherein X is selected from the group consisting of --OH, --OM, --OR 4 , --NH 2 , --NHR 4 , and --N(R 4 ) 2  ; M is a cation selected from the group consisting of Na+, K+, Mg++, Ca++, Zn++, NH 4  +, alkylammonium, dialkylammonium, trialkylammonium, and tetralkylammonium; each R 4  is selected from the group consisting of H, C 1  -C 8  straight or branched chain alkyl, N,N-dimethylaminoethyl, methyl quaternized N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl; and R 5  and R 6  are independently selected from the group consisting of H, C 1  -C 8  straight or branched chain alkyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethyl, and 2-ethoxyethyl;   (ii) B is at least one hydrophilic macromonomer unit, copolymerizable with said A and C units, corresponding to the formula ##STR21## wherein R and R' are independently selected from the group consisting of H and C 1  -C 8  straight or branched chain alkyl; and m is an integer from about 10 to about 2000;   (iii) C is at least one polysiloxane macromonomer unit, copolymerizable with said A and B units, corresponding to the formula   E'(Y).sub.n Si(R.sup.7).sub.3-t (Z).sub.t     wherein E' is an ethylenically unsaturated moiety copolymerizable with A and B; Y is a divalent linking group; R 7  is selected from the group consisting of H, lower alkyl, aryl, or alkoxy; Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least about 500, is essentially unreactive under copolymerization conditions, and is pendant from said backbone after polymerization; n is 0 or 1; and t is an integer from 1 to 3; and     (iv) a is an integer of about 100 or greater, b is an integer of about 2 or greater, and c is an integer of about 1 or greater; and wherein said A units, in conjunction with said ethylenically unsaturated moieties of said B units and said C units, form said backbone; wherein said polymeric portion of said B units forms said hydrophilic side chains; wherein said polymeric portion of said C units forms said polysiloxane side chains; wherein said copolymer has a weight average molecular weight greater than about 10,000, and wherein said copolymer exhibits at least two distinct T g  values, said first T g  corresponding to said backbone and having a value less than about 0° C., and said second T g  corresponding to said hydrophilic polymeric side chains and having a value greater than about 25° C.; and       b) a carrier suitable for application to the skin.   
     
     
       7. A composition according to claim 6 which further comprises a pharmaceutically active agent. 
     
     
       8. A composition for topical application to the skin or useful for delivering pharmaceutical actives to the skin, comprising: a) a water or alcohol soluble or dispersible thermoplastic elastomeric copolymer having a backbone and two or more hydrophilic polymeric side chains and one or more polysiloxane side chains, said copolymer formed from the copolymerization of randomly repeating A, B, and C units and corresponding to the formula    A!.sub.a  B!.sub.b  C!.sub.c     wherein   (i) A is at least one monomer unit, copolymerizable with said B and C units, corresponding to the formula ##STR22## wherein X is selected from the group consisting of --OH, --OM, --OR 4 , --NH 2 , --NHR 4 , and --N(R 4 ) 2  ; M is a cation selected from the group consisting of Na+, K+, Mg++, Ca++, Zn++, NH 4  +, alkylammonium, dialkylammonium, trialkylammonium, and tetralkylammonium; each R 4  is independently selected from the group consisting of H, C 1  -C 8  straight or branched chain alkyl, N,N-dimethylaminoethyl, methyl quaternized N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl; and R 5  and R 6  are independently selected from the group consisting of H, C 1  -C 8  straight or branched chain alkyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethyl, and 2-ethoxyethyl;   (ii) B is at least one hydrophilic macromonomer unit, copolymerizable with said A and C units, corresponding to the formula ##STR23## wherein E is an ethylenically unsaturated moiety, copolymerizable with A, selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzoyl, 4-vinylbenzoyl, and mixtures thereof; R" is selected from the group consisting of hydrogen and C 1  -C 40  straight or branched chain alkyl; R 3  is selected from the group consisting of H, and C 1  -C 8  straight or branched chain alkyl; and m is an integer from about 20 to about 2000;   (iii) C is at least one polysiloxane macromonomer unit, copolymerizable with said A and B units, corresponding to the formula   E'(Y).sub.n Si(R.sup.7).sub.3-t (Z).sub.t     wherein E' is an ethylenically unsaturated moiety copolymerizable with A and B; Y is a divalent linking group; R 7  is selected from the group consisting of H, lower alkyl, aryl, or alkoxy; Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least about 500, is essentially unreactive under copolymerization conditions, and is pendant from said backbone after polymerization; n is 0 or 1; and t is an integer from 1 to 3; and     (iv) a is an integer of about 100 or greater, b is an integer of about 2 or greater, and c is an integer of about 1 or greater; and wherein said A units, in conjunction with said ethylenically unsaturated moieties of said B units and said C units, form said backbone; wherein said polymeric portion of said B units forms said hydrophilic side chains; wherein said polymeric portion of said C units forms said polysiloxane side chains; wherein said copolymer has a weight average molecular weight greater than about 10,000, and wherein said copolymer exhibits at least two distinct T g  values, said first T g  corresponding to said backbone and having a value less than about 0° C., and said second T g  corresponding to said hydrophilic polymeric side chains and having a value greater than about 25° C.; and       b) a carrier suitable for application to the skin.   
     
     
       9. A composition according to claim 8 which further comprises a pharmaceutically active agent.